SI20635A - Method of ammonium sulfate purification - Google Patents
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- SI20635A SI20635A SI9920083A SI9920083A SI20635A SI 20635 A SI20635 A SI 20635A SI 9920083 A SI9920083 A SI 9920083A SI 9920083 A SI9920083 A SI 9920083A SI 20635 A SI20635 A SI 20635A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/18—Preparation by the ammonia-soda process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
Abstract
Description
METODA ZA ČIŠČENJE AMONIJEVEGA SULFATAAMMONIUM SULPHATE CLEANING METHOD
Področje tehnikeThe field of technology
Predmetni izum se nanaša na metodo za čiščenje amonijevega sulfata, natančneje se predmetni izum nanaša na metodo za oblikovanje amonijevega sulfata visoke čistosti z natrijevim sulfatom in natrijevim bikarbonatom s progresivno precipitacijo, brez visokega vnosa energije.The present invention relates to a method for the purification of ammonium sulphate, more particularly the present invention relates to a method for the formation of high purity ammonium sulphate with sodium sulphate and sodium bicarbonate by progressive precipitation without high energy input.
is Ozadje izumais the Background of the Invention
O pripravi natrijevega bikarbonata in amonijevega sulfata se je v obstoječi literaturi obsežno razpravljalo. Eden najkasnejših patentov glede te tehnologije je kanadski patent št. 2.032.627, podeljen 14. januarja 1997 Thompsonu in ostalim.The preparation of sodium bicarbonate and ammonium sulfate has been extensively discussed in the existing literature. One of the latest patents on this technology is Canadian patent no. No. 2,032,627, granted Jan. 14, 1997 to Thompson et al.
so V tem viru je opisan postopek za proizvodnjo natrijevega karbonata in amonijevega sulfata iz natrijevega sulfata, ki obstaja v naravi. Vir se prav tako ukvarja s pripravo dvojne soli natrijevega in amonijevega sulfata. To je vir onesnaževanja, če se trudimo pripraviti sorazmerno čist amonijev sulfat. Prisotnost kakršnekoli dvojne soli in natrija v proizvodu amonijevega sulfata ne stori ničesar drugega kot zmanjša vrednost amonijevega sulfata do take mere, da ni več komercialno zanimiv. V metodologiji je na strani 13, s pričetkom v 8. vrstici, jasno navedeno:so This source describes a process for the production of sodium carbonate and ammonium sulfate from sodium sulfate that exists in nature. The source is also involved in the preparation of double salts of sodium and ammonium sulfate. This is a source of pollution if we are trying to produce relatively pure ammonium sulfate. The presence of any double salt and sodium in the ammonium sulfate product does nothing but reduce the value of the ammonium sulfate to such an extent that it is no longer commercially interesting. The methodology, on page 13, beginning in line 8, clearly states:
s ... slanica, ki ostane po odstranitvi trdnega natrijevega bikarbonata vsebuje mešanico nereagiranega natrijevega sulfata, amonijevega sulfata, amonijevega bikarbonata in manjše količine natrijevega bikarbonata. Ta slanica je s črpalko 36 prenešena v kotel za rekuperacijo plina 31, kjer se jo segreje na temperaturo med 95° in io 100° C. Pod temi pogoji se amonijev bikarbonat razcepi in natrijev bikarbonat, ki je raztopljen v slanici, reagira z amonijevim sulfatom, da nastanejo natrijev sulfat, ogljikov dioksid in amoniak. Ogljikov dioksid in amoniak, ki sta raztopljena v slanici, se odparita, pri čemer v raztopini ostane mešanica, ki je sestavljena zlasti iz is natrijevega in amonievega sulfata. Tako regenerirana ogljikov dioksid in amoniak se ohladi v ohlajevalcu plina 32 ter po dodatnem ohlajanju v ohlajevalcu plina 34 s puhalnikom 33 ponovno uvaja v reaktor 21. Ta regeneracijska stopnja zmanjšuje količino ogljikovega dikosida in amoniaka, ki se uporabljata v postopku.”s ... brine remaining after removal of solid sodium bicarbonate contains a mixture of unreacted sodium sulfate, ammonium sulfate, ammonium bicarbonate and a small amount of sodium bicarbonate. This brine is transferred to a gas recovery boiler 31 by pump 36, where it is heated to a temperature between 95 ° and 100 ° C. Under these conditions, the ammonium bicarbonate is split and the sodium bicarbonate dissolved in the brine reacts with ammonium sulfate. to produce sodium sulfate, carbon dioxide and ammonia. The carbon dioxide and the ammonia dissolved in the brine are evaporated, leaving in the solution a mixture consisting mainly of sodium and ammonium sulphate. Thus regenerated carbon dioxide and ammonia are cooled in the gas cooler 32 and, after further cooling in the gas cooler 34, are again introduced into the reactor by the blower 33. This regeneration step reduces the amount of carbon dicoside and ammonia used in the process. "
Jasno je, da je slanica odparjena in da amonijev sulfat reagira s slanico, da med drugim nastane natrijev sulfat. Razmerje faznega ravnotežja med elementi, ki so prisotni v sistemu, ni bilo priznano.It is clear that the brine is evaporated and that the ammonium sulfate reacts with the brine to produce, among other things, sodium sulfate. The phase balance relationship between the elements present in the system was not recognized.
Spoznanja tega vira prikazujejo le zaprt zančni sistem za sistem nasičene raztopine natrijevega sulfata in amonijevega sulfata. Ta sistem ima lahko za posledico le oblikovanje dvojne soli. Temelječ na spoznanjih tega vira ni mogoč noben drug rezultat. Ta spoznanja so omejena v toliko, s ker se je menilo, da bi lahko razlika v topnosti omogočila proizvod amonijevega sulfata. To ne drži; rezultat je sistem amonijevega sulfata, ki je kontaminiran.The insights from this source only show a closed loop system for the saturated solution of sodium sulfate and ammonium sulfate. This system can only result in the formation of double salt. No other result is possible based on the knowledge of this source. These findings are limited in so far as it was thought that a difference in solubility could make the product of ammonium sulfate possible. This is not true; the result is an ammonium sulfate system that is contaminated.
V ameriškem patentu št. 3.493.329, nosilcev Stiersa in ostalih, so spoznanja usmerjena v pripravo natrijevega bikarbonata in klorovodikove io kisline. Ta cilj je skladen s spoznanji Stiersa in ostalih v 11. stolpcu opisa s pričetkom v 23. vrstici in do 43. vrstice, kjer navajajo naslednje:In U.S. Pat. The 3,483,329 carriers of Stiers et al. Are directed to the preparation of sodium bicarbonate and hydrochloric acid. This objective is consistent with the findings of Stiers et al. In column 11 of the description, beginning in line 23 and line 43, stating the following:
“Če je namesto precipitiranja dvojne soli v prvi fazi postopka prednostna precipitacija amonijevega sulfata, se lahko izvaja naslednji postopek."If precipitating ammonium sulfate is preferable to precipitating the double salt in the first stage of the process, the following procedure may be carried out.
is Če se sedaj sklicujemo na sliko 10, bomo videli, da vsaka od treh krivulj, ki to sliko delijo na tri dele, ustreza simultani precipitaciji dveh soli.is If we now refer to Figure 10, we will see that each of the three curves dividing this image into three parts corresponds to the simultaneous precipitation of the two salts.
Pri vsaki določeni temperaturi je mogoče točko, ki predstavlja sistem, vertikalno prestaviti, tako da se iz raztopine odstrani nekaj vode. Da bi se precipitiral amonijev sulfat namesto dvojne soli, je potrebno postopek izvajati na temperaturi, ki je višja kot na trojni točki, to je okrog 59°C.At any given temperature, the point representing the system can be vertically shifted so that some water is removed from the solution. In order to precipitate ammonium sulphate instead of double salt, the process must be carried out at a temperature higher than at triple point, ie around 59 ° C.
Točka A, ki ustreza približno 63°C, je primerna, ker je zadostno oddaljena od trojne točke, da se izognemo neželjeni precipitaciji dvojne soli, ne da bi bilo potrebno preveč toplote.A point of about 63 ° C is appropriate because it is sufficiently distant from the triple point to avoid unwanted precipitation of the double salt without requiring too much heat.
Jasno je, da na točki A prihaja do simultane precipitacije natrijevega s sulfata in amonijevega sulfata, vendar je to v obliki mešanice obeh soli, ne pa v obliki dvojne soli.”It is clear that at point A there is a simultaneous precipitation of sodium from sulphate and ammonium sulphate, but it is in the form of a mixture of the two salts, not of the double salt. "
Spoznanja iz vira Stiersa in ostalih niso le nezadostna, da bi nekoga navedla k pripravi amonijevega sulfata, ki je čistejši kot 75%, pač pa v tem io viru prav tako ni razkrito nobeno spoznanje o tem, kako posamično pridobiti amonijev sulfat. Vir Stiersa in ostalih nima in ne more imeti za posledico generacije amonijevega sulfata kot posamičnega produkta, kar je jasno mogoče po spoznanjih predmetnega izuma.The findings from Stiers et al. Are not only insufficient to lead someone to prepare ammonium sulfate, which is more than 75% pure, but also do not disclose any knowledge about how to individually obtain ammonium sulfate individually. The source of Stiers and others does not and cannot result in the generation of ammonium sulfate as a single product, which is clearly possible according to the present invention.
Če sledimo metodologiji Stiersa in ostalih, ne moremo pridobiti čistega is produkta amonijevega sulfata, saj ta vir popolnoma spregleda omejitve faznega ravnotežja sistema soli ter zaporedje stopenj, ki si potrebne, da se premaga inherentne kontaminirajoče stopnje, ki so povezane s tem sistemom soli. Čeprav je na sliki 10 Stiersa in ostalih v zvezi s pripravo produkta sklic na točko A, je jasno, da ni nobene navedbe, da produkt neFollowing the methodology of Stiers et al, pure ammonia sulfate product cannot be obtained, since this source completely overlooks the phase equilibrium constraints of the salt system and the sequence of steps required to overcome the inherent contaminating rates associated with this salt system. Although there is a reference to point A in Figure 10 of Stiers and others regarding the preparation of the product, it is clear that there is no indication that the product does not
2o vsebuje mešane soli, kljub temu, da ni navedeno, da bi v mešanici bila kakšna dvojna sol. To se kaže v opisu, kjer Stiers in ostali navajajo, da gre za simultano precipitacijo natrijevega sulfata in amonijevega sulfata. To je skladno s podatki, ki jih navajajo Stiers in ostali v 12. stolpcu, s pričetkom v 21. vrstici. Navedeni niso nobeni podatki, kjer bi bila razvidna količina amonijevega sulfata, obstoječega samega po sebi. V vsakem primeru podatki, ki so navedeni, prikazujejo razmerje precipitata v spojini, kar je med drugim dvojna sol. Končno v besedilu, ki je navedeno v nadaljevanju in se začne v 32. vrstici, Stiers in ostali navajajo naslednje:2o contains mixed salts, although there is no indication that there is any double salt in the mixture. This is reflected in the description where Stiers and others state that there is a simultaneous precipitation of sodium sulfate and ammonium sulfate. This is in line with the information provided by Stiers et al. In column 12, beginning in line 21. No information is provided showing the amount of ammonium sulfate existing per se. In each case, the information provided shows the ratio of precipitate in the compound, which is, among other things, a double salt. Finally, in the text that follows, beginning with line 32, Stiers et al.
... Iz zgoraj navedenega bo razvidno, da je mogoče postopek po izumu izvesti s precipitiranjem amonijevega sulfata v obliki dvojne soli ali kot (NH4)2SO4, skupaj z natrijevim sulfatom, ali z njegovim simultanim precipitiranjem v obliki amonijevega sulfata in v obliki io dvojne soli. ”... It will be apparent from the foregoing that the process according to the invention can be carried out by precipitation of ammonium sulfate in the form of a double salt or as (NH 4 ) 2 SO 4 together with sodium sulfate, or by its simultaneous precipitation in the form of ammonium sulfate and in form io double salt. "
Iz pregleda slik 10 in 11 postane jasno razvidno dejstvo, da se posamezno ne pridobi noben amonijev sulfat. Navedeni niso nobeni podatki za pridobivanje amonijevega sulfata; rezultata izvajanja te metode is sta samo mešana sol in dvojna sol. Z izvajanjem te metode ni mogoče pridobiti ničesar drugega.A review of Figures 10 and 11 shows the fact that no ammonium sulfate is obtained individually. No information is provided for the production of ammonium sulfate; the results of the implementation of this is method are only mixed salt and double salt. Nothing else can be obtained by implementing this method.
Končno je v ameriškem patentu št. 5.830.442, podeljenem 3. novembra 1998 Kresnyaku in ostalim, opisan izboljšan postopek za proizvodnjo amonijevega sulfata. Ta postopek je privlačen, kadar nista bistvena skrb poraba energije in učinkovitost konverzije. V tem postopku se natrijev sulfat odstrani z bistvenim vložkom energije v evaporatorje ter z naknadnim hlajenjem. Rezultat sta sol in raztopina v razmerju 2 :1, pri čemer je nato treba raztopino odpariti, da se pridobi amonijev sulfat. Kot bo opazil izurjen načrtovalec postopkov, ta separacija ustvarja težave glede filtriranja tako velike količine precipitirane dvojne soli. Nadalje je postopek uporabljal tehniko ponovnega raztapljanja dvojne soli in dodajanja le-te v uparjalnik, da se je pridobil natrijev sulfat za reciklirni tok. Ta postopek še povečuje uporabo uparjalnika v celotnem postopku.Finally, in U.S. Pat. No. 5,830,442, granted November 3, 1998 to Kresnyak et al., Describes an improved process for the production of ammonium sulfate. This process is attractive when energy consumption and conversion efficiency are not of major concern. In this process, sodium sulphate is removed by the substantial input of energy into the evaporators and by subsequent cooling. The result is a salt and solution ratio of 2: 1, whereupon the solution must be evaporated to give ammonium sulfate. As one of the skilled process planners will observe, this separation creates the difficulty of filtering such a large amount of precipitated double salt. The process further employed the technique of re-dissolving the double salt and adding it to the evaporator to obtain sodium sulfate for recycling. This process further enhances the use of the evaporator throughout the process.
V predhodnih poskusih, da bi se maksimirali izkoristki in produktivnost, ni bilo ugotovljeno, da bi bila začetna raztopina, vsebujoča natrijev sulfat, premalo nasičena: ta podrobnost je pomembna, da se zagotovi trajanje reakcij, ki so povezane s sintezo amonijevega sulfata.In previous attempts to maximize yields and productivity, the initial sodium sulfate-containing solution was not found to be too saturated: this detail is important to ensure the duration of the reactions associated with the synthesis of ammonium sulfate.
Upoštevaje omejitve, ki jih vsebujejo postopki po znanem stanju, je očitno, da ostaja potreba po postopku, s katerim bo mogoče oblikovati zelo čist amonijev sulfat z viškim izkoristkom, in sicer z uporabo energetsko učinkovitih enot postopka v pravilnem zaporedju. Predmetni izum te cilje izpolnjuje na eleganten način, tako da se po njem oblikujeta is amonijev sulfat in natrijev bikarbonat, ustrezna po farmakopeji ZDA.Considering the limitations contained in the known state of the art processes, it is apparent that there remains a need for a process that can produce very pure high-efficiency ammonium sulfate using the energy efficient process units in the correct order. The present invention fulfills these objectives in an elegant manner by forming ammonium sulfate and sodium bicarbonate, suitable according to the United States Pharmacopoeia.
Industrijska uporabljivostIndustrial usability
Predmetni izum je uporaben v industriji umetnih gnojil.The present invention is useful in the fertilizer industry.
Opis izumaDescription of the invention
Eden od namenov predmetnega izuma je prikazati izboljšan postopek za pripravo amonijevega sulfata in natrijevega bikarbonata, ki je dovolj kakovosten za industrijsko uporabo.One object of the present invention is to provide an improved process for the preparation of ammonium sulfate and sodium bicarbonate of sufficient quality for industrial use.
Nadaljnji namen ene od izvedb predmetnega izuma je prikazati metodo rekuperacije očiščene raztopine amonijevega sulfata iz raztopine natrijevega sulfata, ogljikovega dioksida, amoniaka ali amonijevih ionov, označeno s tem, da ta metoda obsega naslednje stopnje:It is a further object of one embodiment of the present invention to provide a method of recovering a purified solution of ammonium sulfate from a solution of sodium sulfate, carbon dioxide, ammonia or ammonium ions, characterized in that this method comprises the following steps:
a) precipitiranje precipitata natrijevega bikarbonata v najmanj eni stopnji precipitacije, da se poveča koncentracija amonijevega sulfata v raztopini, medtem ko se zmanjša koncentracija natrijevega bikarbonata v raztopini;a) precipitating the sodium bicarbonate precipitate in at least one precipitation step to increase the concentration of ammonium sulfate in solution while reducing the concentration of sodium bicarbonate in the solution;
b) centrifugiranje in spiranje precipitata natrijevega bikarbonata, da se precipitat pretvori v natrijev bikarbonat, ki je dovolj kakovosten za industrijsko uporabo;b) centrifuging and washing the precipitate of sodium bicarbonate to convert the precipitate into sodium bicarbonate of sufficient quality for industrial use;
c) nasičenje raztopine iz stopnje a) z natrijevim sulfatom ali amonijevim bikarbonatom, tako, da se natrijev sulfat ali amonijev bikarbonat doda raztopini pri temperaturi med 35°C in 50°C, in se tako oblikuje drugi precipitiat natrijevega bikarbonata;c) saturating the solution from step a) with sodium sulfate or ammonium bicarbonate by adding sodium sulfate or ammonium bicarbonate to the solution at a temperature between 35 ° C and 50 ° C to form a second precipitate of sodium bicarbonate;
d) obdelava raztopine iz stopnje c) z najmanj enim od naslednjih postopkov: segrevanje raztopine na 95°C, da se sprostita amoniak in ogljikov dioksid ter spravljanje raztopine iz stopnje c) v stik z žveplovo kislino, da se razplini vse karbonatne minerale;d) treating the solution from step c) by at least one of the following processes: heating the solution to 95 ° C to release ammonia and carbon dioxide and bringing the solution from step c) to contact with sulfuric acid to decompose all carbonate minerals;
e) ohlajevanje raztopine iz stopnje d) na temperaturi med -2°C in 2°C, da se oblikuje tretji precipitat natrijevega bikarbonata;e) cooling the solution from step d) to a temperature between -2 ° C and 2 ° C to form a third precipitate of sodium bicarbonate;
f) recikliranje precipitatov iz stopenj d) in e) v stopnjo a);f) recycling of the precipitates from steps d) and e) to step a);
g) obdelovanje raztopine iz stopnje e) z žveplovo kislino, da se razplini vse še obstoječe karbonatne minerale iz natrijevega bikarbonata ter reduciranje natrijevega sulfata na manj kot 7% po teži; ter naknadno s h) rekuperacija očiščene raztopine amonijevega sulfata.g) treating the solution of step e) with sulfuric acid to decompose any existing carbonate minerals from sodium bicarbonate and reducing sodium sulfate to less than 7% by weight; and subsequently by h) recovering the purified ammonium sulfate solution.
Prednostno je dvojna sol, ki so srečamo med formulacijo amonijevega sulfata, v razmerju okrog 0,3 : 1. To ima pomemben vpliv na porabo energije za postopek. Kot primer, zahteva se približno 5 MBtu do 7 MBtu io energije, da se doseže evaporacijo raztopine. Jasno, kjer se razmerje dvojne soli povečuje, se prav tako povečuje vložek energije, ter se tako zmanjšuje učinkovitost postopka. Poleg tega, kjer se ohranja razmerje relativno majhne številke, postane separacija amonijevega sulfata iz natrijevega sulfata občutno lažja, ker se ni treba ukvarjati z velikimi is količinami trdnih snovi dvojne soli za majhno količino tekočega produkta. Na ta način se filtracija poenostavi, brez tveganja, da bo odpovedala oprema ali da bo prišlo do drugih zapletov, ki bi prispevali k zmanjšanju učinkovitosti.Preferably, the double salts encountered during the formulation of ammonium sulfate are in the ratio of about 0.3: 1. This has a significant effect on the energy consumption of the process. As an example, about 5 MBtu to 7 MBtu io of energy is required to achieve evaporation of the solution. Clearly, where the double salt ratio increases, so does the input of energy, thus reducing the efficiency of the process. Moreover, where a relatively small ratio is maintained, separation of ammonium sulphate from sodium sulphate becomes significantly easier, since it is not necessary to deal with large quantities of double salt solids for a small amount of liquid product. In this way, filtration is simplified without the risk of equipment failure or other complications contributing to reduced efficiency.
Naslednji predmet ene od izvedb predmetnega izuma je predstaviti 20 metodo rekuperacije očiščene raztopine amonijevega sulfata iz raztopine natrijevega sulfata, ogljikovega dioksida, amoniaka ali amonijevih ionov, označeno s tem, da ta metoda obsega naslednje stopnje:It is another object of one embodiment of the present invention to present a 20 method of recovering a purified solution of ammonium sulfate from a solution of sodium sulfate, carbon dioxide, ammonia or ammonium ions, characterized in that this method comprises the following steps:
a) precipitiranje precipitata natrijevega bikarbonata v najmanj eni stopnji precipitacije, da se poveča koncentracija amonijevega sulfata v raztopini, medtem ko se zmanjša koncentracija natrijevega bikarbonata v raztopini;a) precipitating the sodium bicarbonate precipitate in at least one precipitation step to increase the concentration of ammonium sulfate in solution while reducing the concentration of sodium bicarbonate in the solution;
b) centrifugiranje in spiranje precipitata natrijevega bikarbonata, da se precipitat pretvori v natrijev bikarbonat, ki je dovolj kakovosten za industrijsko uporabo;b) centrifuging and washing the precipitate of sodium bicarbonate to convert the precipitate into sodium bicarbonate of sufficient quality for industrial use;
c) nasičenje raztopine iz stopnje a) z natrijevim sulfatom ali amonijevim bikarbonatom, tako, da se natrijev sulfat ali amonijev bikarbonat doda raztopini pri temperaturi med 35°C in 50°C, in se tako oblikuje drugi precipitat natrijevega bikarbonata;c) saturating the solution from step a) with sodium sulfate or ammonium bicarbonate by adding sodium sulfate or ammonium bicarbonate to the solution at a temperature between 35 ° C and 50 ° C, thereby forming a second precipitate of sodium bicarbonate;
d) obdelava raztopine iz stopnje c) z najmanj enim od naslednjih postopkov: segrevanje raztopine na 95°C, da se sprostita amoniak in ogljikov dioksid ter spravljanje raztopine iz stopnje c) v stik z žveplovo kislino, da se razplini vse karbonatne minerale;d) treating the solution from step c) by at least one of the following processes: heating the solution to 95 ° C to release ammonia and carbon dioxide and bringing the solution from step c) to contact with sulfuric acid to decompose all carbonate minerals;
e) ohlajevanje raztopine iz stopnje d) na temperaturi med -2°C in 2°C, da se oblikuje tretji precipitat natrijevega bikarbonata;e) cooling the solution from step d) to a temperature between -2 ° C and 2 ° C to form a third precipitate of sodium bicarbonate;
f) recikliranje precipitatov iz stopenj d) in e) v stopnjo a);f) recycling of the precipitates from steps d) and e) to step a);
g) ogrevanje raztopine iz stopnje e) na temperaturo 95°C, da se odvečni natrijev bikarbonat pretvori v natrijev sulfat ter se amoniak in ogljikov dioksid sprostita za recikliranje; ter naknadnog) heating the solution from step e) to a temperature of 95 ° C to convert excess sodium bicarbonate to sodium sulfate and release ammonia and carbon dioxide for recycling; and subsequently
h) rekuperacija očiščene raztopine amonijevega sulfata.h) recovery of the purified ammonium sulfate solution.
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Naslednji predmet ene od izvedb predmetnega izuma je predstaviti metodo oblikovanja amonijevega sulfata iz natrijevega sulfata in natrijevega bikarbonata, označeno s tem, da ta metoda obsega naslednje stopnje:It is another object of one embodiment of the present invention to provide a method of forming ammonium sulfate from sodium sulfate and sodium bicarbonate, characterized in that this method comprises the following steps:
a) preskrba z raztopino natrijevega sulfata;a) supply of sodium sulfate solution;
b) spravljanje raztopine natrijevega sulfata v stik z ogljikovim dioksidom ter amonijakom ali amonijevimi ioni, da se oblikuje prvi precipitat natrijevega bikarbonata ter raztopina, ki vsebuje amonijev sulfat;b) contacting a solution of sodium sulfate with carbon dioxide and ammonia or ammonium ions to form a first precipitate of sodium bicarbonate and a solution containing ammonium sulfate;
c) progresivna precipitacija natrijevega bikarbonata iz raztopine, da se poveča koncentracija amonijevega sulfata in zmanjša koncentracija natrijevega bikarbonata v raztopini;c) progressive precipitation of sodium bicarbonate from the solution to increase the concentration of ammonium sulfate and reduce the concentration of sodium bicarbonate in the solution;
d) rekuperacija prvega precipitata natrijevega bikarbonata kot produkta;d) recovering the first sodium bicarbonate precipitate as a product;
e) centrifugiranje in spiranje prvega precipitata natrijevega bikarbonata, da se pretvori natrijev bikarbonat v natrijev bikarbonat, ki je dovolj kakovosten za industrijsko uporabo;e) centrifuging and washing the first precipitate of sodium bicarbonate to convert sodium bicarbonate to sodium bicarbonate of sufficient quality for industrial use;
f) obdelava raztopine, ki ostane iz stopnje d), z natrijevim sulfatom pri temperaturi med 35°C in 50°C, da se oblikuje drugi precipitat natrijevega bikarbonata;f) treating the solution remaining from step d) with sodium sulfate at a temperature between 35 ° C and 50 ° C to form a second precipitate of sodium bicarbonate;
g) rekuperacija drugega precipitata natrijevega bikarbonata in recikliranje rekuperiranega drugega precipitata v stopnjo b);g) recovery of the second sodium bicarbonate precipitate and recycling of the recovered second precipitate to step b);
-1111-1111
h) obdelava raztopine iz stopnje g) z najmanj enim od naslednjih postopkov: segrevanje raztopine na 95°C, da se sprostita amoniak in ogljikov dioksid ter spravljanje raztopine iz stopnje g) v stik z žveplovo kislino, da se razplini vse karbonatne minerale;h) treating the solution of step g) by at least one of the following processes: heating the solution to 95 ° C to release ammonia and carbon dioxide and bringing the solution from step g) in contact with sulfuric acid to decompose all carbonate minerals;
s i) ohlajevanje raztopine, ki preostane iz stopnje h), na temperaturo med -5°C in 2°C, da se oblikuje tretji precipitat natrijevega bikarbonata ter precipitata natrijevega sulfata in amonijevega sulfata;s i) cooling the solution remaining from step h) to a temperature between -5 ° C and 2 ° C to form a third precipitate of sodium bicarbonate and precipitate of sodium sulfate and ammonium sulfate;
j) rekuperacija tretjega precipitata natrijevega bikarbonata in precipitatov natrijevega sulfata in amonijevega sulfata iz raztopine iz stopnje i) in recikliranje rekuperiranega tretjega precipitata in precipitatov natrijevega sulfata in amonijevega sulfata v stopnjo b);j) recovering the third precipitate of sodium bicarbonate and the precipitates of sodium sulfate and ammonium sulphate from the solution of step i) and recycling the recovered third precipitate and precipitates of sodium sulphate and ammonium sulphate to step b);
k) obdelava raztopine, preostale iz stopnje j), z žveplovo kislino, da se razplini vse ostale karbonatne minerale iz natrijevega bikarbonata in is reducira natrijev sulfat na manj kot 7% po teži; ter naknadnok) treating the solution remaining from step j) with sulfuric acid to decompose all other carbonate minerals from sodium bicarbonate and reducing sodium sulfate to less than 7% by weight; and subsequently
l) rekuperacija očiščene raztopine amonijevega sulfata.l) recovery of the purified ammonium sulfate solution.
Kot posebno prednostna značilnost predmetne metodologije raztopina, preden se je ohladi, vsebuje najmanj 24% amonijevega sulfata, ki takrat, ko je ohlajen, prepreči oblikovanje dvojne soli, ker je učinkovito uporabljena natrijeva sol.As a particularly advantageous feature of the present methodology, the solution, before cooling, contains at least 24% ammonium sulfate, which, when cooled, prevents the formation of a double salt because sodium salt is effectively used.
Še naslednji predmet ene od izvedb predmetnega izuma je predstaviti metodo oblikovanja amonijevega sulfata iz natrijevega sulfata inIt is another object of one embodiment of the present invention to provide a method of forming ammonium sulfate from sodium sulfate and
-1212 natrijevega bikarbonata, označeno s tem, da ta metoda obsega naslednje stopnje:-1212 sodium bicarbonate, characterized in that this method comprises the following steps:
a) preskrba z raztopino natrijevega sulfata;a) supply of sodium sulfate solution;
b) spravljanje raztopine natrijevega sulfata v stik z ogljikovim dioksidom ter amonijakom ali amonijevimi ioni, da se oblikuje prvi precipitat natrijevega bikarbonata ter raztopina, ki vsebuje amonijev sulfat;b) contacting a solution of sodium sulfate with carbon dioxide and ammonia or ammonium ions to form a first precipitate of sodium bicarbonate and a solution containing ammonium sulfate;
c) progresivna precipitacija natrijevega bikarbonata iz raztopine, da se poveča koncentracija amonijevega sulfata in zmanjša koncentracija natrijevega bikarbonata v raztopini;c) progressive precipitation of sodium bicarbonate from the solution to increase the concentration of ammonium sulfate and reduce the concentration of sodium bicarbonate in the solution;
d) rekuperacija prvega precipitata natrijevega bikarbonata kot produkta;d) recovering the first sodium bicarbonate precipitate as a product;
e) centrifugiranje in spiranje prvega precipitata natrijevega bikarbonata, da se pretvori natrijev bikarbonat v natrijev bikarbonat, is ki je dovolj kakovosten za industrijsko uporabo;e) centrifuging and washing the first precipitate of sodium bicarbonate to convert sodium bicarbonate to sodium bicarbonate, which is of sufficient quality for industrial use;
f) obdelava raztopine, ki ostane iz stopnje d), z natrijevim sulfatom pri temperaturi 38°C, da se oblikuje drugi precipitat natrijevega bikarbonata;f) treating the solution remaining from step d) with sodium sulfate at 38 ° C to form a second precipitate of sodium bicarbonate;
g) rekuperacija drugega precipitata natrijevega bikarbonata in recikliranje rekuperiranega drugega precipitata v stopnjo b);g) recovery of the second sodium bicarbonate precipitate and recycling of the recovered second precipitate to step b);
h) obdelava raztopine iz stopnje g) z najmanj enim od naslednjih postopkov: segrevanje raztopine na 95°C, da se sprostita amoniakh) treating the solution of step g) by at least one of the following processes: heating the solution to 95 ° C to release ammonia
-1313 in ogljikov dioksid ter spravljanje raztopine iz stopnje g) v stik z žveplovo kislino, da se razplini vse karbonatne minerale;-1313 and carbon dioxide and bringing the solution from step g) into contact with sulfuric acid to decompose all carbonate minerals;
i) ohlajevanje raztopine, ki preostane iz stopnje h), na temperaturo 2°C, da se oblikuje tretji precipitat natrijevega bikarbonata ter s precipitata natrijevega sulfata in amonijevega sulfata;i) cooling the solution remaining from step h) to a temperature of 2 ° C to form a third precipitate of sodium bicarbonate and of a precipitate of sodium sulfate and ammonium sulfate;
j) rekuperacija tretjega precipitata natrijevega bikarbonata in precipitatov natrijevega sulfata in amonijevega sulfata iz raztopine iz stopnje i) in recikliranje rekuperiranega tretjega precipitata in precipitatov natrijevega sulfata in amonijevega sulfata v stopnjo b);j) recovering the third precipitate of sodium bicarbonate and the precipitates of sodium sulfate and ammonium sulphate from the solution of step i) and recycling the recovered third precipitate and precipitates of sodium sulphate and ammonium sulphate to step b);
k) obdelava raztopine, preostale iz stopnje j), z žveplovo kislino, da se razplini vse ostale karbonatne minerale iz natrijevega bikarbonata in reducira natrijev sulfat na manj kot 7% po teži;k) treating the solution remaining from step j) with sulfuric acid to decompose all other carbonate minerals from sodium bicarbonate and reduce sodium sulfate to less than 7% by weight;
l) odstranitev precipitatov, ki se oblikujejo v raztopini iz stopnje k) inl) removal of the precipitates formed in the solution from step k) and
m) rekuperacija očiščene trdne snovi amonijevega sulfata.m) recovery of the purified ammonium sulfate solid.
Glede oblikovanja natrijevega bikarbonata s centrifugiranjem in spiranjem natrijevega bikarbonata, je rezultat natrijev bikarbonat, ki je dovolj kakovosten za industrijsko uporabo, po standardih farmakopejeConcerning the design of sodium bicarbonate by centrifugation and washing of sodium bicarbonate, the result is sodium bicarbonate of sufficient quality for industrial use, by pharmacopoeia standards
ZDA.USA.
V variaciji postopkov, ki so navedeni, je mogoče uporabiti le eno operacijo precipitacije, namesto vsaj dveh takšnih operacij. To je mogoče doseči z uporabo presežka žveplove kisline, da se odstranijo karbonatne spojine.In the variation of the processes listed, only one precipitation operation can be used instead of at least two such operations. This can be achieved by using an excess of sulfuric acid to remove carbonate compounds.
-1414-1414
Še nadaljnji cilj ene od izvedb predmetnega izuma je predstaviti metodo oblikovanja amonijevega sulfata iz natrijevega sulfata in natrijevega bikarbonata, označeno s tem, da ta metoda obsega naslednje stopnje:It is a further object of one embodiment of the present invention to provide a method of forming ammonium sulfate from sodium sulfate and sodium bicarbonate, characterized in that this method comprises the following steps:
a) preskrba z raztopino natrijevega sulfata;a) supply of sodium sulfate solution;
b) spravljanje raztopine natrijevega sulfata v stik z ogljikovim dioksidom ter amonijakom ali amonijevimi ioni, da se oblikuje prvi precipitat natrijevega bikarbonata ter raztopina, ki vsebuje amonijev sulfat;b) contacting a solution of sodium sulfate with carbon dioxide and ammonia or ammonium ions to form a first precipitate of sodium bicarbonate and a solution containing ammonium sulfate;
c) progresivna precipitacija natrijevega bikarbonata iz raztopine, da se poveča koncentracija amonijevega sulfata in zmanjša koncentracija natrijevega bikarbonata v raztopini;c) progressive precipitation of sodium bicarbonate from the solution to increase the concentration of ammonium sulfate and reduce the concentration of sodium bicarbonate in the solution;
d) rekuperacija prvega precipitata natrijevega bikarbonata kot produkta;d) recovering the first sodium bicarbonate precipitate as a product;
e) centrifugiranje in spiranje prvega precipitata natrijevega bikarbonata, da se pretvori natrijev bikarbonat v natrijev bikarbonat, ki je dovolj kakovosten za industrijsko uporabo;e) centrifuging and washing the first precipitate of sodium bicarbonate to convert sodium bicarbonate to sodium bicarbonate of sufficient quality for industrial use;
f) obdelava raztopine, ki ostane iz stopnje d), z natrijevim sulfatom pri temperaturi od 35°G in 50°C, da se oblikuje drugi precipitat natrijevega bikarbonata;f) treating the solution remaining from step d) with sodium sulfate at a temperature of 35 ° G and 50 ° C to form a second precipitate of sodium bicarbonate;
g) obdelava raztopine iz stopnje f) z najmanj enim od naslednjih postopkov: segrevanje raztopine na 95°C, da se sprostita amoniak in ogljikov dioksid ter spravljanje raztopine iz stopnje f) v stik z žveplovo kislino, da se razplini vse karbonatne minerale;g) treating the solution of step f) by at least one of the following processes: heating the solution to 95 ° C to release ammonia and carbon dioxide and bringing the solution from step f) in contact with sulfuric acid to decompose all carbonate minerals;
-1515-1515
h) ohlajevanje raztopine, ki vsebuje drugi precipitat natrijevega bikarbonata iz stopnje f), na temperaturo med -5°C in 2°C, da se pospešuje precipitat natrijevega bikarbonata ter se oblikujeta precipitata natrijevega sulfata in amonijevega sulfata;h) cooling the solution containing the second precipitate of sodium bicarbonate from step f) to a temperature between -5 ° C and 2 ° C to accelerate the precipitate of sodium bicarbonate and form the precipitates of sodium sulfate and ammonium sulfate;
i) obdelava raztopine, precipitata natrijevega bikarbonata in precipitatov natrijevega sulfata in amonijevega sulfata iz stopnje h) z žveplovo kislino, da se precipitira preostali natrijev bikarbonat;i) treating the solution, sodium bicarbonate precipitate and sodium sulfate and ammonium sulfate precipitates of step h) with sulfuric acid to precipitate the remaining sodium bicarbonate;
j) rekuperacija precipitata natrijevega bikarbonata in precipitatov natrijevega sulfata in amonijevega sulfata iz raztopine iz stopnje i) in recikliranje rekuperiranega natrijevega precipitata in precipitatov natrijevega sulfata in amonijevega sulfata v stopnjo b) inj) recovering the precipitate of sodium bicarbonate and the precipitates of sodium sulfate and ammonium sulfate from the solution of step i) and recycling the recovered sodium precipitate and precipitates of sodium sulfate and ammonium sulfate to step b) and
k) rekuperacija očiščene trdne snovi amonijevega sulfata.k) recovery of purified ammonium sulfate solid.
Še eden od ciljev ene od izvedb predmetnega izuma je predstaviti is metodo desulfuriziranja toka plina, ki vsebuje žveplo, označeno s tem, da ta metoda obsega naslednje stopnje:Another object of one embodiment of the present invention is to present a method of desulfurizing a gas stream containing sulfur, characterized in that the method comprises the following steps:
a) izpostavljanje toka oksidirajočim pogojem, da se je generira spojina, ki vsebuje žveplo;a) subjecting the stream to oxidizing conditions to generate a sulfur-containing compound;
b) spravljanje spojine, ki vsebuje žveplo, v stik z natrijevimb) contacting the sodium-containing compound with sodium
2o bikarbonatom, da se generira natrijev sulfat in2o with bicarbonate to generate sodium sulfate and
c) obdelava natrijevega sulfata po metodi, opisani v zahtevku 1.c) treating sodium sulfate according to the method described in claim 1.
Kratek opis slikShort description of the pictures
-1616-1616
Slika 1 je diagram poteka postopka po znanem stanju;Figure 1 is a flow chart of a known state of the process;
Slika 2 je še en diagram poteka postopka po znanem stanju;Figure 2 is another flow chart of a known state of the process;
Slika 3 je še nadaljnji diagram poteka postopka po znanem stanju;Figure 3 is a further diagram of a known state of the process;
s Slika 4 je diagram poteka postopka po eni od izvedb predmetnega izuma ins Figure 4 is a flow chart of a process according to one embodiment of the present invention and
Slika 5 je nadaljnja izvedba postopka po predmetnem izumu.Figure 5 is a further embodiment of the process of the present invention.
Podobne številke na slikah označujejo podobne elemente.Similar figures in the figures indicate similar elements.
Načini izvedbe izumaMethods of carrying out the invention
Pred razpravo o predmetnem izumu bo narejen splošni povzetek znanega stanja, v povezavi s slikami 1 do 3.Prior to discussing the present invention, a general summary of the known state will be made in conjunction with Figures 1 to 3.
is Slika 1 predstavlja diagram poteka postopka za postopek Thompsona in ostalih.is Figure 1 is a flowchart for the process of Thompson et al.
Diagram poteka postopka Thompsona in ostalih jasno kaže uporabo dveh stopenj procesiranja gnojila, namreč stopnje izparilnika, ki povišuje temperaturo lužne usedline 2b (ML2b) na 100°C, in naknadne ohlajevalne stopnje v fertilizacijskem kristalizatorju pri 60°C. Trdna snov se odstrani kot zahtevani produkt amonijevega sulfata, medtem ko se tekočina iz te stopnje precipitacije naknadno vodi na ohlajevalnik dvojne soli pri 20°C. Tekočina iz stopnje ohlajevanja dvojne soli se nato ponovno uvede vThe flow chart of Thompson et al clearly shows the use of two stages of fertilizer processing, namely, an evaporator step that raises the alkaline sediment temperature 2b (ML2b) to 100 ° C and the subsequent cooling stages in the fertilizer at 60 ° C. The solid is removed as the required product of ammonium sulfate, while the liquid from this precipitation step is subsequently led to a double salt cooler at 20 ° C. The liquid from the double salt cooling stage is then reintroduced into
-1717 evaporator gnojila pri 100°C. V postopku Thompsona in ostalih se je verjelo, da natrijev ion ne bo deloval kot onesnaževalec pri generaciji amonijevega sulfata, če se bo uporabilo razlika v topnosti. Ugotovljeno je bilo, da je to vzrok zapletov in dejansko ponovna uvedba tekočine iz s ohlajevalnika dvojne soli vsebuje natrij in ta je ponovno uveden v odparjevalnik gnojila, da se kontaminira produkt amonijevega sulfata. Na ta način postopek Thompsona in ostalih učinkovito zagotavlja zaprt krog kontaminacije, vendar se navaja, da zagotavlja produkt amonijevega sulfata visoke čistosti. Na osnovi postopka, ki je opisan in o katerem je govora v tem patentu, takega rezultata ni mogoče doseči.-1717 fertilizer evaporator at 100 ° C. In the process of Thompson et al, it was believed that sodium ion would not act as a contaminant in the generation of ammonium sulfate if a solubility difference was used. This was found to be a cause of complications and, in fact, the reintroduction of liquid from the double salt cooler contains sodium and this is reintroduced into the fertilizer evaporator to contaminate the ammonium sulfate product. In this way, the process of Thompson et al effectively provides a closed cycle of contamination, but is said to provide high purity ammonium sulfate product. Based on the process described and discussed in this patent, no such result can be obtained.
Diagram poteka postopka Stiersa in ostalih, ki je orisan na sliki 2, enostavno prikazuje postopek generiranja dvojne soli ali mešane soli, temelječe na podobnih sestavinah, uvodno uvedeno v dobro poznano reakcijo natrijevega bikarbonata. Spoznanja tega vira enostavno is ugotavljajo, kar je bilo poznano že desetletja, ter ne dajejo nobenih navodil osebi, ki je strokovnjak s tega področja, glede sinteze amonijevega sulfata.The flowchart of Stiers et al., Illustrated in Figure 2, simply illustrates the process of generating a double salt or mixed salt based on similar ingredients, initially introduced into the well-known reaction of sodium bicarbonate. The lessons learned from this source simply identify what has been known for decades and provide no guidance to one of skill in the art of ammonium sulfate synthesis.
Na sliki 3 je prikazan postopek Kresnyaka in ostalih. Postopek se opira na bistven vnos energije, da se raztopina segreva, kar ima za posledico precipitacijo natrijevega sulfata in oblikovanje velikih količin precipitata dvojne soli glede na raztopino amonijevega sulfata (2 : 1 razmerje). Postopek, ki je jasno uporaben in ima prednosti, pa ne vsebuje bistvene stopnje, ki je potrebna, da se izognemo visokim stroškom za energijo terFigure 3 shows the procedure of Kresnyak et al. The process relies on the essential energy input to keep the solution warm, resulting in the precipitation of sodium sulfate and the formation of large amounts of double salt precipitate relative to the ammonium sulfate solution (2: 1 ratio). However, the process, which is clearly applicable and has advantages, does not contain the essential level necessary to avoid high energy costs and
-1818 povečamo proizvodnjo amonijevega sulfata: dodatka natrijevega sulfata, da se nasiči raztopina, ki je bila podnasičena. Rezultat takega koncepta je dodatna dostopnost natrija ter sulfata za izboljšane donose amonijevega sulfata in natrijevega bikarbonata.-1818 Increase production of ammonium sulfate: a sodium sulfate supplement to saturate a solution that is unsaturated. The result of this concept is the additional availability of sodium and sulfate for improved yields of ammonium sulfate and sodium bicarbonate.
s Na sliki 4 je prikazan celotni postopek skladno s prvo izvedbo, ki je skupno označen z 10. Uvodoma se v posodi 12 zmešajo voda, amoniak ali vir amonijevih ionov ter ogljikov dioksid, da nastane amonijev bikarbonat. Posodo se lahko ogreje na temperaturo med 20°C in 50°C, prednostno na 30°C. Mešanico se podvrže dvema posamičnima io operacijama precipitacije, da bi se maksimizirala učinkovitost odstranitve natrijevega bikarbonata. V prvi operaciji se amonijev bikarbonat prenese v kristalizacijsko posodo 14, v katero se doda natrijev sulfat iz vira 15, da se oblikuje natrijev bikarbonat. Na tej točki raztopina vsebuje okrog 22% po teži natrijevega bikarbonata. Bikarbonat se prenese v ustalitveno posodo is 16 in na filter 18. Ko je raztopina filtrirana, je njena sestava po teži naslednja: med 13% in 15% amonijevega sulfata, med 13% in 15% natrijevega sulfata in med 8% in 12% natrijevega bikarbonata. Raztopino se nato ponovno zmehča v kašo, tako da se v posodo 20 pri 40°C doda voda. Mešanico se nato centrifugira in spere v centrifugi 22, pri čemer se natrijev bikarbonat naknadno osuši v sušilni stopnji. Filtrat, ki ostane, se prenese v posodo 24 in se naknadno ponovno prenese v posodo 12.s Figure 4 shows the complete process according to the first embodiment, collectively denoted by 10. Initially, water, ammonia or ammonium ion source and carbon dioxide are mixed in container 12 to form ammonium bicarbonate. The container may be heated to a temperature between 20 ° C and 50 ° C, preferably 30 ° C. The mixture is subjected to two separate and precipitating operations in order to maximize the removal efficiency of sodium bicarbonate. In the first operation, the ammonium bicarbonate is transferred to a crystallization vessel 14 to which sodium sulfate from source 15 is added to form sodium bicarbonate. At this point, the solution contains about 22% by weight of sodium bicarbonate. The bicarbonate is transferred to a stabilization vessel 16 and a filter 18. When the solution is filtered, its composition by weight is as follows: between 13% and 15% of ammonium sulfate, between 13% and 15% of sodium sulfate and between 8% and 12% of sodium of bicarbonate. The solution was then again softened into a slurry by adding water to the vessel 20 at 40 ° C. The mixture is then centrifuged and washed in centrifuge 22, with the sodium bicarbonate subsequently dried in the drying step. The remaining filtrate is transferred to container 24 and subsequently re-transferred to container 12.
Po tem, ko se ga centrifugira in spere, natrijev bikarbonat vsebuje 99,80% NaHCO3, z absorbiranim Na2SO4 v koncentraciji 600 ppm. ZAfter being centrifuged and washed, sodium bicarbonate contains 99.80% NaHCO 3 , with Na 2 SO 4 absorbed at a concentration of 600 ppm. Z
-1919 nadaljnjim procesiranjem (Slika 5) je mogoče bikarbonat preoblikovati po standardih farmakopeje ZDA ter ima tako naslednjo sestavo:-1919 further processing (Figure 5), bicarbonate can be transformed to US Pharmacopoeia standards and thus has the following composition:
Natrijev bikarbonat (specifikacija po USP stopnji) s Suha osnovaSodium bicarbonate (USP grade specification) with Dry basis
Natrijev bikarbonat > 99,9 x wt %Sodium bicarbonate> 99,9 x wt%
Natrijev karbonat < xx ppmSodium carbonate <xx ppm
Netopne snovi < xx ppmInsoluble matter <xx ppm
Kalcij (kot Ca) < xx ppm io Magnezij (kot Mg) < xx ppmCalcium (as Ca) <xx ppm io Magnesium (as Mg) <xx ppm
Klorid (kot Cl) < xx ppmChloride (as Cl) <xx ppm
Sulfat (kot SO4) < xx ppmSulphate (as SO 4 ) <xx ppm
Silika (kot Si) < xx ppmSilica (as Si) <xx ppm
Aluminij (kot Al) < xx ppm is Vsebnost vlage < xx wt %Aluminum (as Al) <xx ppm is Moisture content <xx wt%
Filtrat, ki ostane v ustalitveni posodi 16, se prenese v drugo kristalizacijsko posodo 26, v katero se doda brezvoden natrijev sulfat iz vira 28. To je druga operacija precipitacije natrijevega bikarbonata. V tej stopnji raztopina vsebuje približno 15% do 16% kristalov natrijevega bikarbonata. Raztopina in precipitiran natrijev bikarbonat se preneseta v separacijsko pripravo, ki je na primeru prikazana kot ciklonska posoda 29, pri čemer se trdne snovi nato ponovno uvedejo v ustalitveno posodo 16 inThe filtrate remaining in the settling vessel 16 is transferred to another crystallization vessel 26 to which anhydrous sodium sulfate is added from source 28. This is the second precipitation operation of sodium bicarbonate. At this stage, the solution contains about 15% to 16% of sodium bicarbonate crystals. The solution and the precipitated sodium bicarbonate are transferred to a separation apparatus, which is shown as a cyclone vessel 29, for example, and the solids are then reintroduced into the stabilization vessel 16 and
-2020 se filtrat ali raztopina preneseta v posodo 30 pri temperaturi med 35°C in 50°C. Za to operacijo na raztopini je najbolj zaželeno, da se izvaja pri 38°C. Sestava raztopine na tej točki je po teži naslednja: med 18% in 28% amonijevega sulfata, med 5% in 10% natrijevega sulfata ter okrog 8% s natrijevega bikarbonata.-2020 transfer the filtrate or solution to a container 30 at a temperature between 35 ° C and 50 ° C. For this solution operation, it is most desirable to perform at 38 ° C. The composition of the solution at this point is as follows: between 18% and 28% of ammonium sulfate, between 5% and 10% of sodium sulfate, and about 8% of sodium bicarbonate.
Dodatek brezvodnega natrijevega sulfata, kot je bil opisan zgoraj, prispeva k uspehu postopka in predstavlja značilnost, ki je postopki po znanem stanju, kot so bili zgoraj opisani, ne upoštevajo. To pospešuje nasičenje raztopine glede amonijevega sulfata. Predstavlja opazno razliko io glede na znano stanje; v tej fazi je bila v predhodnih tehnikah koncentracija amonijevega sulfata približno 13% po teži (Kresnyak in ostali, zgoraj), kar kaže, da dodatek natrijevega sulfata v predmetnem izumu prispeva k izboljšanju koncentracije amonijevega sulfata. Ta značilnost ima pomembne posledice v postopku ter vodi do večjih is donosov produkta amonijevega sulfata, ne da bi prišlo do težav kontaminacije ali povečanega bremena evaporacije.The addition of anhydrous sodium sulfate, as described above, contributes to the success of the process and is a feature that is not considered by the known processes as described above. This accelerates the saturation of the solution with respect to ammonium sulfate. It represents a noticeable difference io with respect to the known state; at this stage, in prior art, the ammonium sulfate concentration was about 13% by weight (Kresnyak et al., supra), indicating that the sodium sulfate addition of the present invention contributes to the ammonium sulfate concentration improvement. This characteristic has important implications in the process and leads to higher iso yields of the ammonium sulphate product without the problem of contamination or increased evaporation burden.
S procesiranjem raztopine ali filtrata pred to operacijo je raztopina podnasičena glede na natrijev sulfat ter tako dodatek natrijevega sulfata poveča nasičenje amonijevega sulfata. Raztopino se prenese v kristalizator dvojne soli 32, ohladi v ohlajevalniku 34 na temperaturo med 5°C in 2°C, najbolj zaželeno na 2°C. Temperatura je lahko nizka celo do 15°C, vendar pa obstaja praktična omejitev, ker se nasičenje amonijevega sulfata zmanjša pri nižjih temperaturah, kar ovira ekonomiko postopka.By treating the solution or filtrate prior to this operation, the solution is sub-saturated with respect to sodium sulfate and thus the addition of sodium sulfate increases the saturation of ammonium sulfate. The solution is transferred to a double salt crystallizer 32, cooled in a cooler 34 to a temperature between 5 ° C and 2 ° C, most preferably 2 ° C. The temperature may be as low as 15 ° C, but there is a practical limitation because the saturation of ammonium sulfate is reduced at lower temperatures, which impedes the economics of the process.
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Trdne snovi se s filtrom 36 filtrirajo, da se oblikuje pogača. Pogača vsebuje vodo in po teži približno 30% žvepla, 10% natrija in 5% dušika ter jo je mogoče reciklirati v posodo 24. Raztopina vsebuje po teži približno 6% natrijevega bikarbonata, 5% natrijevega sulfata in med 25% in 35% s amonijevega sulfata. V tej stopnji bi bilo mogoče raztopino segreti na okrog 95°C, da bi se sprostila amoniak ali plin ogljikov dioksid.The solids are filtered through filter 36 to form a cake. The cake contains water and by weight about 30% sulfur, 10% sodium and 5% nitrogen and is recyclable in container 24. The solution contains about 6% sodium bicarbonate, 5% sodium sulfate and between 25% and 35% ammonium by weight sulfate. At this stage, the solution could be heated to about 95 ° C to release ammonia or carbon dioxide gas.
Druga možnost je, da se raztopino prenese v posodo 38 ter se jo spravi v stik z žvepleno kislino, da se razplinijo vsi ostali karbonatni minerali iz natrijevega bikarbonata. To se v stroki splošno imenuje “ubitje io bikarbonata”.Alternatively, transfer the solution to the container 38 and contact it with sulfuric acid to decompose all other carbonate minerals from sodium bicarbonate. This is commonly known in the art as "killing io bicarbonate".
Raztopina, ki ostane, se prenese v kristalizacijsko posodo za natrijev sullfat 40, pri temperaturi v razponu, ki je naveden za kristalizator dvojne soli 32, in prednostno pri 2°C, ter se jo ciklonira v ciklonski posodi 42. Trdne snovi se reciklirajo na filtru 36, raztopina, ki je sedaj očiščena is tekočina amonijevega sulfata, pa se shrani v posodi 44. Na tej točki raztopina vsebuje med 3% in 5% natrijevega sulfata po teži in je tako prisotna opazna količina amonijevega sulfata glede na natrijev sulfat. Glede na to razliko je mogoče proizvesti velike količine amonijevega sulfata kot trdne snovi z evaporacijo v odparjalniku 46, ne da bi prišlo do kontaminacije z natrijevim sulfatom. To je mogoče doseči, ker se točki dvojne soli (16 % po teži) natrijevega sulfata jasno izognemo s 3 % do 5 % vsebnostjo natrija po teži. Glede na to se z evaporacijo pri približnoThe remaining solution is transferred to a crystallization vessel for sodium sulphate 40, at a temperature in the range indicated for the crystallizer of double salt 32, and preferably at 2 ° C, and cyclone in a cyclone container 42. The solids are recycled to filter 36, and the solution, which is now purified and the ammonium sulfate liquid, is stored in container 44. At this point, the solution contains between 3% and 5% by weight of sodium sulfate, and thus a noticeable amount of ammonium sulfate relative to sodium sulfate is present. In view of this difference, it is possible to produce large quantities of ammonium sulfate as a solid by evaporation in a evaporator 46 without contamination with sodium sulfate. This can be achieved by avoiding points of double salt (16% by weight) of sodium sulfate with a 3% to 5% sodium content by weight. Accordingly, by evaporation at approx
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110°C izognemo kontaminaciji sulfata, da se omogoči nadzor nad postopkom in kakovost proizvoda.110 ° C avoids sulfate contamination to allow process control and product quality.
Trdni produkt in preostalo tekočino se odvede v ciklonsko posodo 48, pri čemer trdni amonijev sulfat izhaja skozi sušilec 50 in je vsa preostala s tekočina prenesena v posodo 44 za recikliranje, kot je na sliki 4 prikazano s črko A. Proizvod amonijevega sulfata iz sušilca 50 vsebuje manj kot 0,5% po teži natrijevega sulfata ter kot tak predstavlja bistveno izboljšan proizvod, če ga primerjamo s tistimi, ki se sintetizirajo po postopkih iz znanega stanja.The solid product and the residual liquid are discharged into the cyclone vessel 48, with the solid ammonium sulfate flowing through the dryer 50 and any remaining fluid transferred to the recycling vessel 44, as shown in letter 4 by the product A. Ammonium sulfate product from the dryer 50 it contains less than 0.5% by weight of sodium sulphate and, as such, is a substantially improved product when compared with those synthesized by known methods.
io Če se sedaj obrnemo k sliki 5, diagram poteka postopka prikazuje različico postopka, ki je prikazan na sliki 4. Pri tej izvedbi se ne uporablja kristalizator dvojne soli 32, pač pa se uporablja v presežku žveplove kisline, da se zmanjša natrijev bikarbonat v raztopini. Ta varianta postopka je ekonomsko mogoča alternativa, kjer je mogoče žvepleno is kislino dobiti poceni. V tem postopku se raztopina iz posode 30 ogreje na 95°C, da se sprostita plina CO2 in NH3, nato pa se razplinjeno raztopino naknadno ohladi na 0°C. To raztopino se nato uvede v posodo kristalizacije natrijevega sulfata 40, ostale stopnje postopka pa sledijo v skladu s postopkom, ki je nil zgoraj opisan glede slike 4. so Kot primer postopka naslednji primeri prikazujejo uspeh uporabljene metodologije.io Turning to Figure 5 now, the flowchart shows the version of the process shown in Figure 4. In this embodiment, the double salt crystallizer 32 is not used, but is used in excess of sulfuric acid to reduce sodium bicarbonate in solution. . This variant of the process is an economically viable alternative where sulfuric acid can be obtained cheaply. In this process, the solution from vessel 30 is heated to 95 ° C to release CO 2 and NH 3 gases, and then the degassed solution is subsequently cooled to 0 ° C. This solution is then introduced into the sodium sulfate crystallization vessel 40, and the other steps of the process are followed in accordance with the procedure described above with respect to Figure 4. The following examples illustrate the success of the methodology used as an example of the process.
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PRIMER 1 - Trdni kristali NH4HCO3EXAMPLE 1 - Solid crystals of NH4HCO3
Uvedi 1 liter Na2SO4 nasičene slanice pri 38°C specifične gostote 1,300 En liter slanice vsebuje 390 g Na2SO4 v raztopini.Introduce 1 liter of Na 2 SO 4 saturated brine at 38 ° C specific density 1,300 One liter of brine contains 390 g of Na 2 SO 4 in solution.
Predpostavi idealno separacijo trdno / tekočeAssume ideal solid / liquid separation
Prva stopnjaFirst level
390 g/l Na2SO4 + 263,7 g NH4HCO3 150 g/i Na2SO4 + 223 g (NH4)2SO4 + reakcijski produkt # 1390 g / l Na 2 SO 4 + 263.7 g NH 4 HCO 3 150 g / i Na 2 SO 4 + 223 g (NH 4 ) 2 SO 4 + reaction product # 1
125 g/l NaHCO3 + 160 g NaHCO3(5)125 g / l NaHCO 3 + 160 g NaHCO 3 (5)
Izhodna slanica ima sedaj specifično gostoto 1,250 pri 38°C.The source brine now has a specific density of 1,250 at 38 ° C.
Slanico se nato ponovno nasiči z Na2SO4.The brine is then re-saturated with Na 2 SO 4 .
Specifična gostota slanice 1,34 pri 38°C.Specific density of brine 1.34 at 38 ° C.
Slanici se doda 150 g Na2SO4.To the brine is added 150 g Na 2 SO 4 .
Sestava je sedaj : 300 g/l Na2SO4 : 223 g/l (NH4)2SO4 pri 1,340 specifične gostote : 125 g/l NaHC03 The composition is now: 300 g / l Na 2 SO 4 : 223 g / l (NH 4 ) 2 SO 4 at 1,340 specific density: 125 g / l NaHC0 3
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Druga stopnjaSecond level
Zdaj se doda: 190 g NH4HCO3.Now add: 190 g NH4HCO3.
Nova sestava slanice:New brine composition:
: 384 g/l (NH4)2SO4 : 127 g/l Na2SO4 : 102,8 g/l NaHCO3 : 384 g / l (NH 4 ) 2 SO 4 : 127 g / l Na 2 SO 4 : 102.8 g / l NaHCO 3
Produkt:Product:
204,6 g reakcijskega produkta # 2 + 22,2 nasičenje redukcija 226,8 g NaHCO3 204.6 g of reaction product # 2 + 22.2 saturation reduction 226.8 g of NaHCO 3
Reakciji # 1 +#2 Rekuperirani produkt: 160 + 226,8 = 386,8 g NaHCO3 na liter Na2SO4 uvedene raztopine.Reactions # 1 + # 2 Recovered product: 160 + 226.8 = 386.8 g NaHCO 3 per liter Na 2 SO 4 solutions introduced.
Ohlajevalna stopnjaCooling rate
Slanica se ohladi na 0°C in se filtriraThe brine was cooled to 0 ° C and filtered
Trdne snovi so trdne snovi mokre pogače ter vsebujejo hidrate Na2SO4, 20 (NH4)2SO4 in NaHCO3, ki se reciklira v stopnjo 1 ali stopnjo 2.Solids are wet cake solids and contain Na 2 SO 4 , 20 (NH 4 ) 2 SO 4 and NaHCO 3 hydrates, which are recycled to Level 1 or Level 2.
Ta mokra pogača je: Na2SO4- 10 H2O = 144,7 g (NH4)2SO4-8H2O = 71,2This wet cake is: Na 2 SO 4 - 10 H 2 O = 144.7 g (NH 4 ) 2 SO 4 -8H 2 O = 71.2
-2525-2525
NaHCO3-10 H,O = 87.4 Hidrati H2O so prevzeti: 303, gNaHCO 3 -10 H, O = 87.4 Hydrates H 2 O assumed: 303, g
Ti hidrati so prikladen način, da se odstrani voda za recikliranje, kar 5 zmanjšuje evaporacijsko breme.These hydrates are a convenient way to remove recycling water, reducing the evaporation load.
Skupni rekuperirani NaHCO3je: 409 + 27,8 + 436,8 gTotal recovered NaHCO 3 is: 409 + 27.8 + 436.8 g
Konverzijska učinkovitost postopka Na2SO4 v NaHCO3je: io uvedena snov = 540 g; izhodna slanica = 62,5 g + 75 x 142 (Na2SO4 npr.)The conversion efficiency of the Na 2 SO 4 process in NaHCO 3 is: io substance introduced = 540 g; output brine = 62.5 g + 75 x 142 (At 2 SO 4 eg)
84(2)84 ( 2 )
Izhodna slanica = 126, gOutlet brine = 126, g
Učinkovitost tokokroga = 76,6 %.Circuit efficiency = 76.6%.
is Ubitje bikarbonatais Killing of bicarbonate
62,5 g Na2S04 62.5 g Na 2 S0 4
350 g (NH4)2SO4 + 43,7 g H2SO4 ® CO2 75 g NaHCO3 350 g (NH 4 ) 2 SO 4 + 43.7 g H 2 SO 4 ® CO 2 75 g NaHCO 3
Nova sestava slanice:New brine composition:
126 g Na2SO4 + vrela raztopina H2SO4 350 g (NH4)2SO4 126 g Na 2 SO 4 + boiling solution H 2 SO 4 350 g (NH 4 ) 2 SO 4
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Raztopino se spet ohladi na 0°C 1,24 specifične gostoteThe solution was again cooled to 0 ° C at 1.24 specific density
GlauberjevaGlauber's
62.5 g Na2SO4 + 143 g Na2SO4 10 H2O62.5 g Na 2 SO 4 + 143 g Na 2 SO 4 10 H 2 O
350 g (NH4)2SO4 350 g (NH 4 ) 2 SO 4
827.5 g H2O827.5 g H 2 O
Glauberjeva sol se reciklira v stopnjo 1 ali 2.Glauber salt is recycled to grade 1 or 2.
Slanica se odparjuje, dokler ni v izhodu 16 % Na2SO4 Slanica doseže pri 60°C, specifično gostoto 1,320.The brine is evaporated until it is 16% at Na 2 SO 4. The brine reaches a specific density of 1,320 at 60 ° C.
g Na2SO4 g At 2 SO 4
122.5 g (NH4)2SO4 donos (NH4)2SO4 = 227,5 g/l snovi, uvedene v evaporator122.5 g (NH 4 ) 2 SO 4 yield (NH 4 ) 2 SO 4 = 227.5 g / l substance introduced into the evaporator
245 g H2O skupaj 437,5 g245 g of H 2 O total 437.5 g
Slanico se reciklira v ubitje bikarbonata, se ohladi, da bi se odstranil Na2SO4.The brine is recycled to kill bicarbonate, cooled to remove Na 2 SO 4 .
-2727-2727
PRIMER 2EXAMPLE 2
Kot bo razvidno, je postopek zlasti primeren za desulfurizacijo tokov, ki s vsebujejo žveplo. Tokove enostavno izpostavimo oksidirajočim pogojem, da se generira spojina, ki vsebuje žveplo, ki se jo naknadno kontaktira z natrijevim bikarbonatom, da se oblikuje natrijev sulfat. V tem pogledu sta s sklicevanjem vključena ZDA patenta 5.830.422 in 5.654.351. Oksidacijo SO3 v SO4 je mogoče doseči z razpršitvijo zraka ali z uporabo oksidanta, io kot sta peroksid ali ozon. Kovine je mogoče precipitirati tudi z enostavnimiAs will be seen, the process is particularly suitable for desulfurization of sulfur containing streams. Currents are easily exposed to oxidizing conditions to generate a sulfur-containing compound subsequently contacted with sodium bicarbonate to form sodium sulfate. In this regard, U.S. Patent Nos. 5,830,422 and 5,654,351 are incorporated by reference. Oxidation of SO 3 to SO 4 can be achieved by air dispersion or by the use of an oxidant such as peroxide or ozone. Metals can also be precipitated by simple ones
CO3 ali sulfidnimi redukcijami in filtracijo.CO 3 or sulfide reductions and filtration.
NH4HCO3 (z uporabo Na2SO4 anhidrita)NH4HCO3 (using Na 2 SO 4 anhydrite)
Nasičena raztopina NH4HCO3 pri 30°C vsebuje 263,7 g/l NH4HCO3. Zato:Saturated NH4HCO3 solution at 30 ° C contains 263.7 g / l NH4HCO3. Therefore:
I raztopine + 390 g Na2SO4 —»· ΔΗI solutions + 390 g Na 2 SO 4 - »· ΔΗ
150 g Na2SO4(i) 223 g (NH4)2SO4(i)+ 125 g CO3(i) + 160 g NaHCO3(S) ΔΗ dodati toploto (I) tekočina (s) trdna snov150 g Na 2 SO 4 (i) 223 g (NH4) 2 SO4 (i) + 125 g CO 3 (i) + 160 g NaHCO 3 ( S ) ΔΗ add heat (I) liquid (s) solid
-2828-2828
Slanico se ponovno nasiči s 150 g Na2SO4, da se pridobi slanico, ki ima 1,34 pri 38°C.The brine was re-saturated with 150 g of Na 2 SO 4 to obtain a brine having 1.34 at 38 ° C.
NH3 in CO2je mogoče dodati kot plin ali kot NH4HCO3 trdno snov, da se reakcija zaključi.NH 3 and CO 2 can be added as gas or as NH 4 HCO 3 solid to complete the reaction.
s Zdaj se doda 190 g NH4HCO3.s 190 g of NH 4 HCO 3 is now added.
Nova sestava slanice ProduktNew Brine Composition Product
384 g/l (NH4)2SO4 204,6 g NaHCO3 384 g / l (NH 4 ) 2 SO 4 204.6 g NaHCO 3
127 g/l Na2SO4 io 80 g NaHCO3 127 g / l Na 2 SO 4 and 80 g NaHCO 3
Primarni donos postopka 160 + 204,6 = 364,6 g NaHCO3.The primary yield of the process is 160 + 204.6 = 364.6 g of NaHCO 3 .
Čeprav so bile izvedbe izuma zgoraj opisane, izum ni omejen le na is te izvedbe ter bo osebam, ki so strokovnjaki na tem področju, očitno, da veliko število modifikacij predstavlja del predmetnega izuma, v kolikor se ne oddaljujejo od duha, narave in obsega izuma, kot je razviden iz zahtevkov in iz opisa.Although the embodiments of the invention have been described above, the invention is not limited to this embodiment, and it will be apparent to those skilled in the art that a large number of modifications form part of the present invention insofar as they do not depart from the spirit, nature and scope of the invention , as can be seen in the claims and in the description.
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| US10396898P | 1998-10-13 | 1998-10-13 | |
| PCT/CA1999/000902 WO2000021886A1 (en) | 1998-10-13 | 1999-09-30 | Method of ammonium sulfate purification |
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| CN102198953A (en) * | 2011-04-07 | 2011-09-28 | 四川金圣赛瑞化工有限责任公司 | Methods for coproducing sodium carbonate and ammonium sulfate from melamine tail gas and mirabilite |
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| US4268492A (en) * | 1979-08-06 | 1981-05-19 | Pennzoil Company | Process for production of potassium sulfate and hydrochloric acid |
| US4371512A (en) * | 1981-02-03 | 1983-02-01 | Pennzoil Company | Production of alkali metal sulfates |
| JPS57205315A (en) * | 1981-06-15 | 1982-12-16 | Chisso Corp | Reducting method for amount of chlorine contained in modified potassium sulfate by very small amount |
| FR2523114A1 (en) * | 1982-03-11 | 1983-09-16 | Alsace Mines Potasse | PROCESS FOR PRODUCING POTASSIUM SULFATE FROM SOLUTIONS CONTAINING MAGNESIUM CHLORIDE AND POTASSIUM CHLORIDE |
| JPS58161917A (en) * | 1982-03-19 | 1983-09-26 | Onoda Kagaku Kogyo Kk | Manufacture of potassium sulfate |
| US4562058A (en) * | 1983-08-02 | 1985-12-31 | International Minerals & Chemical Corp. | Process for crystallizing potassium sulfate |
| US4588573A (en) * | 1983-09-27 | 1986-05-13 | Prodeco, Inc. | Method for the production of potassium sulfate using sulfuric acid and potassium chloride |
| US4554151A (en) * | 1983-09-27 | 1985-11-19 | Prodeco, Inc. | Process for producing K3 H(SO4)2 crystals and potassium sulfate crystals |
| IT1174208B (en) * | 1984-06-19 | 1987-07-01 | Italkali | PROCEDURE FOR THE PRODUCTION OF POTASSIC SULPHATE AND MAGNESIA POTASSIC SULPHATES GRANULATED, AND GRANULATED SO PRODUCED |
| US4707347A (en) * | 1985-04-17 | 1987-11-17 | Kali Und Salz | Process for the production of potassium sulfate from potassium chloride by means of ion exchangers |
| US4844874A (en) * | 1987-11-12 | 1989-07-04 | Quad Environmental Technologies Corp. | Method and means for controlling mist scrubber operation |
| FR2638108B1 (en) * | 1988-10-26 | 1991-02-08 | Solvay | PROCESS FOR REMOVING A RESIDUE COMPRISING SODIUM SULFATE |
| CA2032627C (en) * | 1990-12-18 | 1997-01-14 | Jack S. Thompson | Process for producing sodium carbonate and ammonium sulphate from sodium sulphate |
| US5654351A (en) * | 1990-12-18 | 1997-08-05 | Ormiston Mining And Smelting Co. Ltd. | Method for sodium carbonate compound recovery and formation of ammonium sulfate |
| US5298050A (en) * | 1992-10-09 | 1994-03-29 | Great Salt Lake Minerals Corporation | High water solubility potassium sulfate and method of producing same |
| US5366534A (en) * | 1992-11-30 | 1994-11-22 | Sherritt Inc. | Granular potassium sulfate preparation and process for production thereof |
| US5552126A (en) * | 1994-11-28 | 1996-09-03 | Dead Sea Works Ltd. | Co-production of potassium sulfate, sodium sulfate and sodium chloride |
| US5549876A (en) * | 1994-11-28 | 1996-08-27 | Dead Sea Works | Production of potassium sulfate using differential contacting |
| US5529764A (en) * | 1994-11-28 | 1996-06-25 | Dead Sea Works Ltd. | Co-production of potassium sulfate and sodium sulfate |
| US5830422A (en) * | 1995-06-23 | 1998-11-03 | Ormiston Mining And Smelting Co. Ltd. | Method for production of sodium bicarbonate, sodium carbonate and ammonium sulfate from sodium sulfate |
-
1999
- 1999-05-13 US US09/310,995 patent/US6106796A/en not_active Expired - Fee Related
- 1999-09-29 CA CA002284969A patent/CA2284969A1/en not_active Abandoned
- 1999-09-30 HU HU0104345A patent/HUP0104345A3/en unknown
- 1999-09-30 JP JP2000575799A patent/JP2002527329A/en active Pending
- 1999-09-30 EA EA200100341A patent/EA200100341A1/en unknown
- 1999-09-30 WO PCT/CA1999/000902 patent/WO2000021886A1/en not_active Application Discontinuation
- 1999-09-30 NZ NZ510785A patent/NZ510785A/en unknown
- 1999-09-30 SK SK501-2001A patent/SK5012001A3/en unknown
- 1999-09-30 CZ CZ20011177A patent/CZ20011177A3/en unknown
- 1999-09-30 PL PL99347034A patent/PL347034A1/en unknown
- 1999-09-30 YU YU27001A patent/YU27001A/en unknown
- 1999-09-30 SI SI9920083A patent/SI20635A/en unknown
- 1999-09-30 KR KR1020017004657A patent/KR20010088871A/en not_active Application Discontinuation
- 1999-09-30 BR BR9914548-0A patent/BR9914548A/en not_active Application Discontinuation
- 1999-09-30 CN CNB998143774A patent/CN1177759C/en not_active Expired - Fee Related
- 1999-09-30 TR TR2001/00966T patent/TR200100966T2/en unknown
- 1999-09-30 ID IDW00200101050A patent/ID28731A/en unknown
- 1999-09-30 CN CNA021462305A patent/CN1491890A/en active Pending
- 1999-09-30 EP EP99945815A patent/EP1124756A1/en not_active Withdrawn
- 1999-09-30 AU AU58455/99A patent/AU765320B2/en not_active Ceased
-
2000
- 2000-01-01 ZA ZA200001143A patent/ZA200001143B/en unknown
- 2000-03-07 HR HR20000126A patent/HRP20000126A2/en not_active Application Discontinuation
-
2001
- 2001-04-10 NO NO20011850A patent/NO20011850L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1330611A (en) | 2002-01-09 |
| NZ510785A (en) | 2003-11-28 |
| JP2002527329A (en) | 2002-08-27 |
| AU5845599A (en) | 2000-05-01 |
| CZ20011177A3 (en) | 2001-09-12 |
| AU765320B2 (en) | 2003-09-18 |
| EA200100341A1 (en) | 2002-04-25 |
| YU27001A (en) | 2003-10-31 |
| KR20010088871A (en) | 2001-09-28 |
| CN1491890A (en) | 2004-04-28 |
| SK5012001A3 (en) | 2001-10-08 |
| CA2284969A1 (en) | 2000-04-13 |
| EP1124756A1 (en) | 2001-08-22 |
| NO20011850L (en) | 2001-06-13 |
| HUP0104345A2 (en) | 2002-03-28 |
| ZA200001143B (en) | 2000-11-21 |
| CN1177759C (en) | 2004-12-01 |
| WO2000021886A1 (en) | 2000-04-20 |
| ID28731A (en) | 2001-06-28 |
| US6106796A (en) | 2000-08-22 |
| HUP0104345A3 (en) | 2003-01-28 |
| HRP20000126A2 (en) | 2001-02-28 |
| PL347034A1 (en) | 2002-03-11 |
| BR9914548A (en) | 2001-06-26 |
| NO20011850D0 (en) | 2001-04-10 |
| TR200100966T2 (en) | 2001-09-21 |
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